JPH03202856A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To accelerate the start of electrification of a positively chargeable toner in a high-speed machine, to stabilize the chargeability of the toner and to improve the aggregation resistance by adding a specified electrification controlling agent. CONSTITUTION:This toner is composed essentially of a colorant, a thermoplastic resin such as styrene-acrylic resin, an electrification controlling agent selected among compds. represented by formulae I-VI and nonmagnetic inorg. fine particles such as hydrophobic silica. In the formulae I-VI, each of R1-R6 and R10-R14 is H, alkyl, etc., M is Zn, Fe, etc., in the formula I and Zn, Cr, etc., in the formula II, X is halogen or an ionic residue, n1 2, 4 or 6, R7 is 8-30C alkyl, each of R8 and R9 is H, lower alkyl, etc., n2 is an integer of >=1, each of R15 and R16 is H, alkyl, etc., and R17 is alkyl, aryl, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. This invention relates to an excellent toner, especially a positively chargeable toner.

PRIOR ART AND ITS PROBLEMS Development of electrostatic latent images involves electrostatically applying negatively or positively triboelectrically charged toner to an electrostatic latent image having a positive or negative charge formed on a photoreceptor using various methods. The developed image is then fixed by transferring and fixing the toner image onto the transfer paper. This toner is first required to have an appropriate amount of charge in order to obtain a clear developed image without fogging or the like. Furthermore, it is also required that the amount of charge does not change over time, and that changes such as significant attenuation or solidification of the amount of charge do not occur due to environmental changes, such as changes in humidity. This is because when the amount of charge attenuates from the initially set value and becomes smaller, toner scattering increases, causing problems such as background fog, toner scattering on blank areas, and toner stains around the developing device. be.

In order to meet the above requirements, a charge control agent is usually added during the production of toner, but recently color toners have become more popular, and a white or pale yellow charge control agent with excellent color reproducibility is required.

Colorless, white, or pale yellow negative charge control agents that impart a negative charge are commercially available and are highly effective, and there are no practical restrictions on the use of these control agents. However, there are only a few known positive charge control agents that can be used in color toners, such as colored nigrosine dyes, white quaternary ammonium salts, or imidazole compounds. .

Nigrosine dyes do not consist of a single pure compound, but are a mixture of several compounds, and their exact composition is unknown, which poses a problem as they cannot always be expected to have the same level of functionality.

Further, regarding color toners, there are problems in applying nigrosine dyes because they are colored.

When used alone, quaternary ammonium salts have poor charging performance,
In particular, it is inferior in charge build-up, durability stability, and environmental stability.

Furthermore, electrophotographic copiers and printers are becoming faster, but in high-speed machines, it is necessary to uniformly charge the toner in a single period of time, so developing devices that can perform strong agitation and mixing, which places strong stress on the developer, are required. It is necessary to use it. Furthermore, in order to improve the fixing properties in high-speed machines, it is necessary to lower the viscosity of the resin, which also tends to cause deterioration in charging properties and cohesive properties. Therefore, if a toner made of a conventional charge control agent or other composition is applied as is, there are problems such as the developer becoming spent or agglomerating in the developing device.

In particular, as organic photoreceptors have become longer in life and more sensitive, organic photoreceptors have come to be used even in high-speed copying machines, and positively charged toners for high-speed copying machines have therefore become very important.

Problems to be Solved by the Invention As mentioned above, there are only a few positive charge control agents that impart a positive charge, and colorless or white ones suitable for color toners are particularly desired.

The present invention has been made in view of the above circumstances, and provides a toner with excellent long-term charge stability, especially in a high-speed machine with a developing device that mixes and stirs strongly, and has excellent charge build-up and ensures stable chargeability. In addition, it is an object of the present invention to provide a toner having excellent anti-aggregation properties.

Another object of the present invention is to provide a positively charged toner that has excellent color reproducibility and excellent translucency.

Means for solving the problem, that is, the present invention is characterized by comprising at least a colorant, a thermoplastic resin, a charge control agent selected from the group consisting of the following general formulas [1] to [VI], and nonmagnetic inorganic fine particles. Toner for developing electrostatic images with general formula II]; 1 [In the formula, R1, R2, and R1 represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and each may be the same or different; M is Zn, Fes
Represents a metal such as Co, N1, Cu or Hg; X represents a halogen atom or a monovalent ionic residue: nI is 2.4
．． 6 is an integer, and M is Fe.

2 or 4 if Ni, 2 if M is Cu or Co.
4 or 6, and 2 when M is ZnlHg. Imidazole metal complex represented by 1; General formula [■1: 4 [wherein R6 and R6 are hydrogen atoms, alkyl groups,
Represents an aralkyl group or an aryl group, each of which may be the same or different: M is Zn, Fe,
Represents Co, Ni%CuSCr or Hg. ] An imidazole metal compound represented by the general formula [■1; R,,R,.

[In the formula, R1° and Ro represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and each may be the same or different. ] Imidazole derivatives represented by the general formula [V]: R7 [wherein R2 is an alkyl group having a carbon number of C to C1°, R1 and R9 are a hydrogen atom, a lower alkyl group, an aralkyl group or an aryl group. may be the same or different. ] Imidazole derivative represented by the general formula [■1; [in the formula R1! , R13 and R14 represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and Zn2, which may be the same or different, represents an integer of 1 or more. ] Imidazole derivative general formula [■1; [wherein, RISs RIB represents hydrogen, an alkyl group, an aralkyl group, or an aryl group which may have a substituent; R17 represents an alkyl group, an aralkyl group, or Represents an aryl group, each group may have a substituent 1
Regarding ゜.

In general formulas [1] and [II], R2, R1, R3, R
4, R3 and R1 are a hydrogen atom, an alkyl group of c1 to CXS (which may be branched), an aralkyl group such as benzyl or phenethyl, or an aryl group such as a phenyl group, and may be the same or different. You can.

X represents a halogen atom or a monovalent ionic residue such as nitric acid or acetic acid.

nl represents an integer of 2.4 or 6, and M is Fe.

It is 2 or 4 in the case of Ni, 2.4 or 6 if M is Cu or Co, and 2 if M is Zn or Hg.

The imidazole metal complex represented by the general formula [I] is prepared by dissolving an imidazole compound and a metal salt represented by MX, [M and X are the same as above] in an alcohol solvent such as methanol or ethanol, or an aromatic solvent such as benzene or toluene. By reacting at reflux temperature for 3 to 20 hours, a white powder can be made into synthetic leather.

The imidazole metal complex compound represented by the general formula [I[] can be prepared by superheating the imidazole metal complex represented by the general formula [I], or by combining the imidazole compound and MX.
Synthetic leather can also be made by dissolving a metal salt represented by , in a solution such as ethanol or acetone, and heating and refluxing the solution for a long time.

The general formula [I] of the present invention and the imidazole metal complex compound represented by [I] are exemplified below, but are not limited thereto.

[+-25] [+-26] +11113 shi+ynzs [+-49] [+-501 [+1-3] [1[-4] [ri-9] [l-10] wrinkle 1111 Shini [+-39] [1-43] [+-45] [+-47] [1 11] [+-401 [+-44] [1-461 [+-48] [■ 12] [■ 23] [■-24] [+-59] [+-60] [+-611 [+-62] [1r-351 [+-551 [1-56] [+-57] [+-581 CIIHI% Wrinkle eyes.

(+-69] [+-70] [+-711 [+-72] [r-75] [+-76] [+-77] [+-791 [1-78F [■ 36] [11-371 [1-80] (Hereinafter, blank space) [ll-56] [n-57] In general formula [11[]; R is C, an alkyl group having a carbon number of ~C8°; R8
and R9 are each a lower alkyl group of hydrogen atoms CI' to Ctss, an aralkyl group such as benziti or 7-enethyl, or an aryl group such as phenyl, and may be the same or different.

Many of the compounds represented by the general formula [111F] are known per se, and can be prepared using generally known methods, such as Japanese Patent Publication No. 42
It is a material that is made into synthetic leather according to the method described in Publication No. 1548 and the like.

Examples of the imidazole derivative represented by the general formula [1+1] include, but are not limited to, the following.

[111-15] [m-17] Wrinkle 1123 General formula [in IVJ; 11 R11R11 RIM or Ro is a hydrogen atom, an alkyl group of C3 to CSS (which may be branched), an aralkyl group such as benzyl or phenethyl, or an aryl group such as a phenyl group, which may be the same or different.

The container can be synthesized by reacting the imidazole compound represented by the general formula [IV] with formaldehyde directly or using a suitable solvent and a strong inorganic alkali catalyst.

As the solvent used in the synthesis, alcohols such as methanol, ethanol, impropatol, ethylene glycol, and ethylene glycol monoalkyl ether are preferred. The reaction temperature is 80-200℃ depending on the type of solvent.
is appropriate.

The derivatives represented by the general formula [IV] of the present invention include the following, but are not limited thereto.

(Hereinafter, blank space) 16nlH 1+zBn71 In the general formula [V], R18, R13 or R14 in the general formula [V] is a hydrogen atom, an alkyl group of 01 to C1 (which may be branched), benzyl or phenethyl, etc. are an aryl group such as an aralkyl group or a phenyl group, and may be the same or different.

In the general formula [Vl, n2 is an integer of 1 or more, preferably 1 to
It is an integer of 50.

The imidazole derivative represented by the general formula [V] and the imidazole derivative represented by the general formula [B] and the general formula [C]
Synthetic leather can be easily obtained by reacting the imidazole derivative represented by the formula with paraformaldehyde directly or using an appropriate solvent in the presence of a strong inorganic alkali catalyst; In formula 1, R+□, R. and R14 are the same as above. 1. Solvents used for synthetic leather include methanol, ethanol,
Alcohols such as impropatol, ethylene glycol monoalkyl ether and ethylene glycol are preferred. The reaction temperature is 80-200℃ depending on the type of solvent.
°C is appropriate.

The derivatives represented by the general formula [V] of the present invention include the following, but are not limited thereto.

C and below, blank space) General formula [VI] Ro and R11 are hydrogen atoms, 01 to CSS alkyl groups (
R1!, which may be branched), aralkyl such as benzyl or 7-enethyl, or aryl group such as phenyl group, and which may have a substituent! x R1@ may be the same or different.

RIF is an alkyl group (which may be branched) of 01 to C□, an aralkyl group such as benzyl or phenethyl, or an aryl group such as a phenyl group, and each group may have a substituent. Especially R.I.

The longer the chain, the higher the charge level.

The imidazole derivative represented by the general formula [VI] is obtained by reacting the imidazole compound represented by the general formula [D] with acrylonitrile as shown in the following formula to obtain a compound of the general formula [E], and then reacting with dicyandiamide. It can be easily synthesized by

Some of the compounds are also known as curing agents for epoxy resins.

The imidazole derivatives represented by the general formula [Vrl of the present invention include the following, but are not limited thereto.

CI, CH.

Imidazole compounds represented by general formulas [I] to [VI] have excellent charge build-up, stability, environmental resistance, etc., and are useful as charge control agents for toners.
It is particularly used as a charge control agent for positively chargeable toners with excellent color reproducibility and translucency.

General formula [! The properties of the imidazole compounds represented by [VI] to [VI] include that they are 1I-soluble in the toner due to the constitution of the thermoplastic resin constituting the toner.

In addition, when the thermoplastic resin is a homopolymer as a monomer, it also refers to its 7-mer, and in the case of a copolymer, it refers to a monomer mixture mixed in the 7-mer ratio of the copolymer, or a 7-mer as the main component. . For example, when the thermoplastic resin is a styrene-acrylic resin, it is referred to as styrene monomer, when it is an acrylic resin, it is referred to as the main component acrylic monomer, and when it is a polyester resin, it is referred to as ethylene glycol. Even when other resins are used, seven resins are selected based on the above concept.

In the present invention, "slightly soluble" is defined as the presence of insoluble matter when the charge control agent is dispersed in 50019 to 100 g of Nanatsumar, and preferably the presence of insoluble matter when 250 mi of the charge control agent is dispersed in 1009. . The fact that the charge control agent is poorly soluble in monomers allows the charge control agent to be present in the form of particles in the thermoplastic resin constituting the toner or on the surface of the toner. Generally, it is considered desirable that the charge control agent be completely compatible with the thermoplastic resin constituting the toner to form a homogeneous system from the viewpoint of uniformly charging the toner. However, for low-melting point, low-viscosity resins used in toners for high-speed machines, toners for low-temperature fixing, or transparent color toners, the charge buildup is slow and it takes time to reach the saturated charge amount, or the printing life is short. Sometimes, the change in the amount of charge becomes large, causing a problem that stable chargeability cannot be obtained. On the other hand, Nanatsuma
By using a charge control agent that is poorly soluble in toner particles, strongly charged points can be formed on the toner surface by charge control agent particles, and the above-mentioned problem of charge buildup can be solved. Furthermore, when a charge control agent that is incompatible with the thermoplastic resin is used, the charge stability is not sufficiently improved, and furthermore, it is difficult to improve the heat resistance and agglomeration resistance of toners using low melting point and low viscosity resins. This is a big problem, but the present invention has stabilized the charge, improved heat resistance, and improved anti-aggregation properties by using a charge control agent (A) and appropriate inorganic fine particles with different charge levels. can be improved.

Non-magnetic inorganic solid particles include silica, colloidal silica, hydrophobic silica, talc, bentonite, alumina, silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, and tungsten carbide. , chromium carbide, molybdenum carbide, diamond, boron nitride, titanium nitride, zirconium nitride, titanium boride, zirconium boride, iron oxide, chromium oxide, titanium oxide, calcium carbonate, magnesium oxide, carborundum disulfide, molybdenum heptadide Various heptadides such as magnesium, various metal soaps such as aluminum stearate, zinc stearate, calcium stearate, etc. are used.

It is also desirable to use these inorganic fine particles after being subjected to hydrophobic treatment.

The charge control agent selected from the group consisting of imidazole compounds represented by the general formulas (11 to [VI] (hereinafter simply referred to as "charge control agent" unless otherwise specified) and nonmagnetic inorganic fine particles may be a known toner, For example, it can be applied to pulverized toner, suspension polymerized toner, capsule toner, etc.

The charge control agent and the nonmagnetic inorganic fine particles may be contained inside the toner, or may be attached and fixed to the surface of the toner.

When it is contained inside, in addition to additives such as colorants, a charge control agent and non-magnetic inorganic fine particles may be further added to prepare a pulverized toner, suspension polymerization toner, capsule toner, etc. by a conventional method. In the case of a capsule toner, it is desirable to prepare the toner so that the outer shell layer contains the charge control agent.

In addition, in an embodiment in which the charge control agent and nonmagnetic inorganic fine particles are attached to the surface of the outer shell layer, they are attached to the above-mentioned toner surface by the action of van der Waals force and electrostatic force, and then by mechanical impact force or the like. It should be fixed.

Apparatus that can be suitably used in such a method include the hybridization system (manufactured by Nara Kikai Seisakusho Co., Ltd.) that applies the impact method in high-speed airflow, Ongmill (manufactured by Honkawa Micron Co., Ltd.), and Mechanomill (manufactured by Doen Seiko Co., Ltd.). (manufactured by). However, it is of course not limited to this method.

The content of charge control agent depends on the type of toner, toner additives,
The binder resin should be selected appropriately depending on the type of binder resin and the toner development method (two-component or one-component), etc., but if it is incorporated into the toner by a pulverization method or suspension method, the toner structure IR resin The amount is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight per 100 parts by weight. If the amount is less than 0.1 part by weight, the desired amount of charge cannot be obtained, and if it is more than 20 parts by weight, the amount of charge becomes unstable and the fixing performance deteriorates.

When using the charge control agent by adhering and fixing it to the toner surface, the amount is 0°001 to 10% per 100 parts by weight of toner particles.
Parts by weight are used, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.

If the amount is less than o and oot parts by weight, the amount of charge control agent present on the surface of the toner particles will be small, resulting in insufficient charge, and 10
When the amount is more than 1 part by weight, adhesion of the charge control agent to the toner surface becomes insufficient, and peeling of the charge control agent from the toner surface during use becomes a problem.

When a charge control agent is attached and fixed on the toner surface, a stable charge can be imparted by using a very small amount as described above, and it is also compatible that the imidazole compound of the present invention is white or light-colored. As a result, it is possible to provide a color toner that has excellent charging performance and is capable of forming clear color images.

The charge control agent is 5μ when it is contained inside the toner.
m or less, preferably 3 μm or less, more preferably 1 μm
Use with particle size below 100 yen. If a particle size larger than 5 μm is used, the state of dispersion with the inorganic fine particles shown in the present invention becomes non-uniform, making it difficult to stabilize the charge amount and heat resistance properties. 1μ when attaching the charge control agent to the toner surface
The particle size is preferably 0.5 μm or less, more preferably 0.5 μm or less.

If a particle size larger than 1 μm is used, it will spread evenly onto the toner surface.
This is disadvantageous in terms of adhesion and fixation.

The charge control agent may be used in combination with other charge control agents.

Further, in order to stabilize chargeability, a very small amount of a charge control agent of opposite polarity may be added. When the charge control agent of the present invention is used in combination with other charge control agents as described above, the total amount thereof should be within the above-mentioned usage range.

The amount of non-magnetic inorganic fine particles added varies depending on the type of inorganic compound, particle size, etc., and also depends on the type of toner, toner additives,
It varies depending on the type of binder resin, the type and amount of charge control agent, etc., but generally when it is incorporated into the toner by a pulverization method, suspension polymerization method, etc., the amount is 0.0% per 100 parts by weight of toner resin. 01 to IO parts by weight, preferably 0.1 to 5 parts by weight. 0.0! If it is less than 10 parts by weight, the desired effect on heat resistance will be small, and if it is more than 10 parts by weight, charging properties and fixing properties will deteriorate.

In addition, in the case where the outer shell layer contains inorganic fine particles in a laminated structure, 0.000 parts by weight per 100 parts by weight of toner particles.
001 to 1 part by weight, preferably 0.001 to 1 part by weight. Use 0.5 parts by weight of Ol. If the content is less than 0.001 part by weight, the effect on the desired heat resistance will be small, and if the content is more than 1 part by weight, charging properties and fixing properties will deteriorate.

Furthermore, when considering the ratio of the amount of charge control agent and non-magnetic inorganic fine particles added, it is found that the amount of non-magnetic inorganic fine particles added is 1-100 parts by weight for 100 parts by weight of charge control agent.
It is used in an amount of 10 to 80 parts by weight, more preferably 20 to 50 parts by weight. If the proportion of the charge control agent exceeds the above range, the agglomeration resistance at high temperatures and high humidity will deteriorate, and if the proportion of nonmagnetic inorganic fine particles exceeds the above range, the charge stability at high temperatures and high temperatures will deteriorate.

Furthermore, when considering the relationship between the average particle size of the charge control agent and the non-magnetic inorganic fine particles, it is possible to use a combination of non-magnetic inorganic fine particles that are 1/4 or less of the average particle size of the charge control agent. preferable. When the ratio is larger than 1/4, charge stability deteriorates.

The resin constituting the toner is not particularly limited as long as it is commonly used as a binder in toners. It will be done. styrene resin,
Thermoplastic resins such as (meth)acrylic resins, olefin resins, amide resins, carbonate resins, polyethers, polysulfones, polyester resins, and epoxy resins, or thermoplastic resins such as urea resins, urethane resins, and epoxy resins. thermosetting resins, copolymers and polymer blends thereof, and the like are used. Note that the composite FR used in the toner for developing electrostatic latent images of the present invention
IIWI includes not only those in a complete polymer state, such as in thermoplastic resins, but also those in an oligomer or prepolymer state, such as in thermosetting resins, as well as partially prepolymer and crosslinking agents. It is also possible to use those containing the following.

Specifically, the seven polymers constituting the resin used in the present invention are listed below. That is, examples of vinyl monomers include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
1) n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, pn-nonylstyrene, pn-decylstyrene, p-n-F7'silstyrene, p -methoxystyrene, p-7 dinylstyrene, p-chlorostyrene, 3
．． Examples include styrene and its derivatives such as 4-dichlorostyrene. Examples of other vinyl monomers include ethylene, ethylenically unsaturated monoolefins such as propylene, butylene, and isobutylene, vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride, vinyl acetate, Vinyl esters such as vinyl propionate, vinyl benzoate, vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic acid 2-ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl a-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, propyl methacrylate ,
σ of n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc.
- Methylene aliphatic monocarboxylic acid esters, (meth)acrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc., vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, vinyl Examples include vinyl ketones such as xyl ketone and methyl isopropenyl ketone, N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone, and vinylnaphthalenes.

Monomers for obtaining amide resins include caprolactam, tribasic acids include terephthalic acid, isophthalic acid, adipic acid, maleic acid, succinic acid, cepatic acid, thioglycolic acid, and diamines. Examples include ethylene diamine, diaminoethyl ether, 1,4-diaminobenzene, 1,4-diaminobutane, and the like.

Examples of diisocyanates for obtaining a urethane resin include p-phenylene diisocyanate, p-xylene diisocyanate, and 1,4-tetramethylene diisocyanate, and examples of glycols include ethylene glycol, diethylene glycol,
Examples include propylene glycol and polyethylene glycol.

Examples of diisocyanates for obtaining a urea resin include p-phenylene diisocyanate, p-xylene diisocyanate, 1,4-tetramethylene diisocyanate, and examples of diamines include ethylene diamine, diaminoethyl ether, .4
-diaminobenzene, 1,4-diaminobutane, and the like.

In addition, examples of amines for obtaining an epoxy resin include ethylamine, butylamine, ethylenediamine, 4-diaminobenzene% 1% 4-diaminobutane, and monoethanolamine, and examples of epoxies include: Examples include diglycidyl ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and hydroquinone diglycidyl ether.

In addition, as a monomer for obtaining a polyester-based sI fat, as a polyol component, ethylene glycol, diethylene glycol, triethylene glycol, 1.2-propylene glycol, 1.3-propylene glycol, 1
．． 4-butanediol, 1,3-butanediol, 2,
3-butanediol, 1,5-bentanediol, l,
6-hexanediol, neopentyl glycol, 2-
Ethyl l.

3-hexanediol, 2.2.4-trimethyl-1,
3-bentanediol, 1,4-bis(2-hydroxymethyl)cyclohexane, 2,2-bis(4-hydroxypropoxyphenyl)propane, bisphenol A1
Examples include hydrogenated bisphenol A, polyoxyethylated bisphenol A, and polybasic fi [parts include maleic acid, fumaric acid, mesaconic acid, citraconic acid,
Unsaturated carboxylic acids such as itaconic acid, glutacone, 1.2.4-benzenetricarboxylic acid, 1.2.5-benzenetricarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, malonic acid,
Sebacic acid, 1,2.4-cyclohexanetricarboxylic acid, 1,2.5-cyclohexanetricarboxylic acid, 1,
Examples include saturated carboxylic acids such as 2.4-butanetricarboxylic acid and l,3-dicarboxy-2-methyl-2-methylcarboxypropane, and acid anhydrides thereof and esters with lower alcohols may also be used. , Specifically, for example, maleic anhydride, phthalic anhydride, tetrahydroheptalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromo heptadalic anhydride, dimethyl terephthalate, etc. can be mentioned. In addition, the polyester resin used in the present invention is not limited to the one obtained by polymerizing a combination of one type each of the polyol component and other basic acid component as described above, but it may be one obtained by polymerizing using multiple types of each. is also good, especially polynucleotide 1
As 1J*min, unsaturated carboxylic acid and saturated carboxylic acid m.
Alternatively, polycarboxylic acids and polycarboxylic anhydrides are often combined.

It is desirable to further add a low molecular weight polyolefin wax to the thermoplastic resin, and the amount thereof is 1-10 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the thermoplastic resin.
It is 6 parts by weight. For these compositions, the imidazole compound disclosed by the present invention exhibits good ability to control positive chargeability and can impart practically sufficient chargeability.

Recently, there has been a demand for technology that allows for even faster copying.
Toners used for such high-speed development need to be improved in their ability to be fixed to transfer paper or the like in a short time and their separability from the fixing roller. Therefore, the homopolymer or copolymer synthesized from the above-mentioned (meth)acrylate system, or the above-mentioned polyester-based resin used in high-speed development has a number average molecular weight (Mn), a weight average molecular weight (M w ), the relationship with the 2-average molecular weight (Mz) is i. ooo≦Mn≦7,000 40≦My/Mn≦70 200≦Mz/Mn≦500, and further 2 for number average molecular weight (Mn).

It is preferable to use one in which 000≦Mn 7 and O'0 0.

Toner Structure 1j It exhibits negative chargeability as a characteristic, making it difficult to use as a positively chargeable toner resin. When these polyester resins are used in translucent toners, it is desirable to use linear polyesters with a glass transition temperature of 55 to 70°C, a softening point of -15000, and a molecular weight distribution (Mw/Mn) of 3 or less. . When used as an oil-less fixing toner, the glass transition temperature is 55-80°C, the softening point is 80-150°C, and the weight is 15-20wt.
, % gelling component is desirable. However, the imidazole compounds represented by the general formulas [I] to [VI] of the present invention exhibit good positive charge control ability even for such polyester resins, and can impart practically sufficient chargeability.

Moreover, the imidazole compounds represented by the general formulas [I] to [VI] of the present invention are mainly composed of a linear urethane-modified polyester (C) obtained by reacting a linear polyester resin (A) with a 4-diisocyanate (B). It is also possible to impart a practically good positive charge control ability to a toner composed of a resin as a component. Note that the linear urethane-modified polyester referred to here is composed of dicarboxylic acid and diol,
0.3 to 0.95 mol of diisocyanate (B) per mol of linear polyester resin (A) having a number average molecular weight of 1000 to 20,000 and an acid value of 5 or less and whose terminal groups are essentially hydroxyl groups. The main component is a linear urethane-modified polyester resin (C) obtained by the reaction, and the resin (C) has a glass transition temperature of 40 to 80°C and an acid value of 5 or less. As the dicarboxylic acid, diol and diincyanate, those mentioned above can be used.

As the colorant contained in the toner for developing electrostatic latent images of the present invention, various organic and inorganic pigments and dyes of various colors as shown below can be used.

That is, examples of black pigments include carbon black, copper oxide, manganese dioxide, aniline black, and activated carbon.

Yellow pigments include yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel suelona 7 tall yellow 51 banzer yellow 01 banzer yellow 10G, benzidine yellow 〇1 benzidine yellow GR, quinoline yellow lake. , Hermanent Yellow NCG, and Tartrazine Lake Nat.

Orange pigments include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, palkan orange, and industhrene brilliant orange RK.
, Benzidine Orange G1 Indus Thread Brilliant Orange GK, etc.

Red pigments include red pigment, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, lithol red, pyrazolone red, watching red, calcium salt, lake red D1 brilliant carmine 6B, eosin lake, rhodamine lake B1 alizarin lake. , Brilliant Carmine 3B, etc.

Examples of violet pigments include manganese violet, 7 asto violet B1 methyl violet lake, and the like.

Examples of blue pigments include navy blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free 7 thalocyanine blue, partially chlorinated 7 thalocyanine blue, 7 earth sky blue, and industhrene blue BC.

Examples of green pigments include chrome green, chromium oxide, pigment green B1 malachite green lake, and final yellow green G.

Examples of white pigments include zinc white, titanium oxide, antimony, and zinc sulfide.

Extender pigments include pallite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

In addition, various dyes such as basic, acidic, dispersed, and direct dyes include nigrosine, methylene blue, rose bengal,
They include quinoline yellow and ultramarine blue.

These colorants can be used alone or in combination, and may be used in an amount of 1 to 20 parts by weight based on the total weight of the synthetic resin contained in the core particle and the total weight of the synthetic resin contained in the outer shell layer. , more preferably 2 to 10 parts by weight. That is, if the amount is more than 20 parts by weight, the fixing properties of the toner will deteriorate, while if it is less than 1 part by weight, the desired image density cannot be obtained.

When used as a translucent color toner, various pigments and dyes of various colors as shown below can be used as the coloring agent.

Yellow pigments include c, t, 10316 (naphthol yellow S), C, 1, 11710 (hansa yellow 10G)
,C,! , 11660 (Hansa Yellow 5G), C, 11
1670 (Banzae 17-3G), C, 1, 11680
(Hansa Yellow G), C, 1, 11730 (Hansa Yellow GR), (, 1, 11735 (Hansa Yellow A), C
, 1, 11740 (Hansa Yellow RN), c, x, 12
710 (Hansa Yellow R), C, 1, 12720 (Pigment Yellow), C, 1, 21090 (Benzidine Yellow), C, 1, 21095 (Benzidine Yellow),
C, 1, 21100 (benzidine yellow GR), c, t
,20040(Permanent Yellow NCG),C,1,
21220 (Parkan 7 Astro Yellow 5), c, r',
21135 (Parkan Fast Yellow R), etc.

Red pigments include c, r, 12055 (Stalin I), c, r, 12075 (permanent orange),
c, r, 12175 (Resol 7 Ast Orange 3GL
), c, r, 12305 (permanent orange GTR
), c, r, l 1725 (Hansa Yellow 3R), c,
r, 21165 (Palcan Fast Orange GG), c
, t, 21110 (benzidine orange G), c, t,
12120 (Permanent Red 4R), C, 1, 12
70 (rose red), C-1, 12085 (7y yearled), 1. r, l 2315 (Brilliant Fast Scarlet), C, 1,1231O (Permanent Red F2R), C, 1,12335 (Permanent Red F4R), C, 1,12440 (Permanent Red FRL), CA, 12460 (Permanent Red F
RLL), c, x, 12420 (Permanent Erode F4RH), C, I-12450 (Light Fast Red Toner B), C, 1,12490CI<- Manent Carmine FB), C, r, 15850 (Brilliant Carmine 6B) )and so on.

Examples of blue pigments include C, 1, 74100 (metal-free phthalocyanine blue), c, r, 74160 (phthalocyanine blue), and c, r, 74180 (fast sky blue).

These colorants can be used alone or in combination, but are used in an amount of 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of the resin contained in the toner particles.
It is desirable to use parts by weight; that is, if it is more than 10 parts by weight, the toner's fixing properties and translucency will decrease, while if it is less than 1 part by weight, there is a risk that the desired image density may not be obtained. It is.

The toner of the present invention may contain an anti-offset agent in order to improve fixing properties. Various waxes, especially low molecular weight polypropylene, polyethylene,
Alternatively, polyolefin waxes such as oxidized polypropylene and polyethylene are preferably used. Furthermore, these waxes have a number average molecular weight (M n ) of 10
00-20000 and a softening point (Tm) of 80-150°C is preferable. If the number average molecular weight Mn is 1000 or less or the softening point TII+ is 80°C or less, uniform dispersion with the synthetic resin component in the synthetic resin coating layer will not be possible, and only the wax will be eluted onto the toner surface, causing the toner to deteriorate. This may not only cause unfavorable results during storage or development, but also may cause contamination of the photoreceptor such as filming. Furthermore, if the number average molecular weight exceeds 20,000 or To+ exceeds 150° C., not only will the compatibility with the resin deteriorate, but the effects of containing wax such as high temperature offset resistance will not be obtained. Further, from the viewpoint of compatibility, waxes having polar groups are desirable when used together with synthetic resins having polar groups.

In the toner of the present invention, the following inorganic fine particles may be further used as a post-processing agent in order to improve fluidity. Examples of such inorganic fine particles include silica, aluminum oxide, titanium oxide, silica-aluminum oxide mixture, and silica-titanium oxide mixture.

The toner of the present invention can be applied to both two-component developers and acid-component developers (magnetic and non-magnetic).

When used as a two-component developer, known carrier powders such as ferrite carriers, coating carriers, iron powder carriers, and carriers having a composite charging surface can be used.

To prepare the toner for developing an electrostatic image according to the present invention, the charge control agent and non-magnetic inorganic fine particles according to the present invention are mixed with a thermoplastic resin, a pigment or dye as a coloring agent, a magnetic material as necessary, and other materials. Additives, etc. are thoroughly mixed using a ball mill or other mixer, and then melted, kneaded, and kneaded using a heat kneader such as a heated roll or kneader to make the resins compatible with each other. Pigments or dyes are then dispersed in the mixture. Alternatively, a toner having a desired average particle size can be obtained by dissolving, cooling and solidifying, and then pulverizing and classifying.

Alternatively, the material can be obtained by dispersing the material in a binder resin solution and then spray-drying it, or by mixing the specified material with the monomers that should constitute the binder resin to form a suspension and then polymerizing it. A polymerization toner manufacturing method for obtaining a toner, a so-called microcapsule toner consisting of a core material and a shell material, and a method in which the toner is contained in the core material, the shell material, or both can be applied.

Furthermore, it can also be effectively used in a method in which a charge control agent or nonmagnetic inorganic fine particles are attached to the surface layer by the action of van der Waals force and electrostatic force, and then fixed by mechanical impact force or the like.

Toners prepared by these methods can be used for developing to visualize electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. by any conventionally known means.

Example 1 Thermoplastic styrene-acrylic (St/nBMA=7/3) resin Mn; 4200 Mw; 210.900 Mz; 1
323000 My/Mn; 50.2Mz/Mn;
315 Tg=62℃ Weight parts 00 Softening point 115℃ Acid value 25.8 ・Carbon black 8 (manufactured by Mitsubishi Chemical Industries, Ltd.; MA#8) ・Low molecular weight polypropylene 3 (manufactured by Sanyo Chemical Industries, Ltd.: Viscol 605 P) ・Compound [■-
571 (white, fine powder, 1μm) 5. Hydrophobic silica (12mμm) R9742 (manufactured by Nippon Aerosil Co., Ltd.) The above materials were thoroughly mixed in a ball mill, then kneaded on three rolls heated to 140°C, and the mixture was left to stand. After cooling,
After finely pulverizing with a feather mill, the powder was further classified to obtain toner A having an average particle size of 10 μm.

Examples 2 to 6 In Example 1, instead of compound [l-57], [I[42] (0.8 μm) and [l-61] (1°0
μm), [IV-4] (0.8 pta), [V-4]
(0,8 μm), [I 36] (0,8, u+o]:
Toners BF were manufactured using the same composition method except for the modified El.

Comparative Example 1 Toner G was prepared in the same manner as in Example 1, except that Bontron N-01 (manufactured by Orient Chemical Industries, Ltd.) (2 μm) was used instead of Compound [l-57].

Comparative Example 2 Toner H was prepared in the same manner as in Comparative Example 1 except that hydrophobic silica R-974 was not added.

Comparative Example 3.4 Hydrophobic silica R-97 in Example 3 and Example 4
Toners (1) and (J) were prepared in the same manner as in Example 3 and Example 4, except that toner No. 4 was not added.

Example 7 In Example 11, thermoplastic S! Thermoplastic W1 polyester resin (Mn; 3400, My; 213,400
, Mz; 1,183,200, Mvt/Mn; 62
-8, Mz/Mn: 348, acid value: l 6.7, softening point: 109°C, Tg: 64°C) and hydrophobic titanium oxide T-805 instead of hydrophobic silica R-974 as non-magnetic inorganic fine particles. Toner K was obtained using the same composition and method except that (X30 mμ manufactured by Degussa) was used.

Example 8 Part by weight Polyester resin 100 (manufactured by Kao Corporation; Tufton NE-382) Brilliant Carmine 6B 3 (CN
5850) The above materials were thoroughly mixed in a ball mill and then kneaded on three rolls heated to 140°C. After cooling the kneaded material,
The mixture was coarsely ground using a No. 7 Ether mill, and further finely ground using a jet mill. Thereafter, air classification was performed to obtain a fine powder i with an average particle size of 10 μm.

Furthermore, compound [l-55] (0.8 μa
+) and 1.0 parts by weight of hydrophobic silica R-976 (7
+sμ) (manufactured by Nippon Aerosil Co., Ltd.) and 0.3 parts by weight of MMA/iBMA (=1:9) particles (MP-4951X
Manufactured by Shinken Kagaku Co., Ltd.; Average particle size 0.2 μm 1 Glass transition temperature 8
Put 15 parts by weight (5℃) into a Henschel mixer and mix 1.5 parts by weight.
The mixture was mixed and stirred for 2 minutes at a rotational speed of 0.00 rpm to electrostatically adhere the compound [l-551 and other microparticles to the surface of the colorant-containing resin particles. Next, treatment was performed at 6000 rpm for 3 minutes using Nara Kikai)\Ibridization System NH5-Im to form a resin film layer containing compound [1-55] and hydrophobic silica on the surface of the colorant-containing resin particles, and the average Toner L with particle size 1lp11
I got it.

Example 9 In Example 8, hydrophobic alumina RX-C (20μ
Same composition except for changing to mX (manufactured by Nippon Aerosil Co., Ltd.),
Toner M was obtained by the method.

Example 10 Monodispersed spherical styrene and n-butyl methacrylate copolymer obtained by seed weight method (average particle size 6 μm, glass transition temperature 54°C: softening point 128°C, gelling component (toluene insoluble component) 15% Contains) 100 parts by weight and carbon black (manufactured by Mitsubishi Chemical Industries, Ltd.: MA#8)
8 parts by weight and 10 parts by weight of St/nBMA (7:3) particles (average particle size; 0.2μ; glass transition temperature: 85°C) were placed in a IOQ Henschel mixer and mixed and stirred for 2 minutes at a rotation speed of 150 Qrpm to form a polymer. Carbon black was attached to the surface of the particles. Next, using a Nara Mechanical Hybridization System ANMS-1 model at 7200 rpm.
The carbon black was fixed on the surface of the polymer particles by treatment for 3 minutes.

Furthermore, polymer particles 1 treated with the above carbon black
00 parts by weight and MMA/i BMA (1:
9) 20 parts by weight of particles MP-4951 (manufactured by Soken Kagaku Co., Ltd.: average particle size 0°2 μm; glass transition temperature 85°C) and 0.5 parts by weight of R-972 (16 μm) (manufactured by Nippon Aerosil Co., Ltd.)
A resin coat layer was provided by the same treatment as above except that the processing conditions of the hybridization system were 7200 rpm+ for 5 minutes.

Furthermore, a positive charge control agent compound [I-42] (0.8 μ■) was added to 100 parts by weight of the polymer particles obtained here.
By subjecting 0.5 parts by weight of fine particles of (white, fine powder) to the same treatment as above with a carbon black layer formed, the fine particles of compound [11-42] were fixed to the toner surface, and the average particle size was 6. .5μ positive, sphericity 132, coefficient of variation 8%
Toner N was obtained.

Example 11 In Example 8, hydrophobic titanium oxide T-805 (
30 parts 1 (manufactured by Degussa) and further replaced with the positive charge control agent compound [■-55] [l-36] (1,0
μm) 1 part by weight and quaternary ammonium salt P-51 (L, S
μ+s) (manufactured by Orient Chemical Industry Co., Ltd.) Using the same composition and method except that 0.5 parts by weight was used, the average particle size was 11μ.
I got Toner R from the company.

Comparative Example 5.6.7 Toner 0, P,
I got Q.

The constituent components of the toners prepared in Examples 1-10 and Comparative Examples 1-7 are summarized in Table 1 below.

(Hereinafter, blank) [Manufacture of carrier] In order to subject the toner to the evaluation described below, a binder type carrier was manufactured as follows.

Ingredients: ・Polyester resin 100 (manufactured by Kao Corporation: NE-1110) ・Inorganic magnetic powder 500 (manufactured by Toda Industries, Ltd., EPT-1000) ・Carbon black 2 (manufactured by Mitsubishi Chemical Corporation, MA#8) Above materials was thoroughly mixed and pulverized using a Henschel mixer, and then the cylinder part was heated at 180°C and the cylinder head part was heated to 170°C.
The mixture was melted and kneaded using an extrusion mixer set at ℃. After cooling, the mixed material was finely pulverized using a jet mill and then classified using a classifier to obtain a magnetic carrier having an average particle size of 55 μm.

[Particle Size Measurement] Particle size measurements of toner and carrier were performed as follows.

(1) Carrier particle size The carrier particle size is Microtrack model 7995-1.
Measurement was performed using 0sRA (manufactured by Nikkiso Co., Ltd.), and the average particle size was determined.

(2) Toner Particle Size The average particle size of the toner was determined by measuring the relative weight distribution by particle size with a 100 μm aperture tube using a Coulter Counter (manufactured by Coulter Counter).

(3) The charge control agent and nonmagnetic inorganic fine particles were measured by determining the average value of the secondary particle diameter using a scanning electron microscope (SEM).

Evaluation method for various properties Examples 1-10 and Comparative Example 1 thus obtained
Toner A-R of ~7 was post-treated with 0.2 parts by weight of colloidal silica R-972 (manufactured by Aerosil Co., Ltd.) per 100 parts by weight of each toner, and the toners obtained here were - "Used for evaluation of various characteristics.

In addition, for the purpose of knowing the influence of inorganic fine particles on the toner properties when they are contained in the toner (in the case of the present invention) and the inorganic fine particles when simply mixed with the toner in post-processing, we will explain about Toner L and Toner O. conducted the same evaluation as O for toner without post-treatment (Example 12).
8 and Comparative Example 8).

Charge amount (Q/M) and scattering amount Here, 42 g of the surface-treated toner and 558 g of the carrier described above were placed in a 2a plastic bottle and placed on a rotating stand.
The amount of charge on the toner was measured when the toner was rotated at 0 Orpm.

At the same time, the amount of scattering was measured in the following manner.

The amount of scattering was measured using a digital dust meter model P5H2 (manufactured by Shibata Chemical Co., Ltd.). The dust meter and the magnet roll are combined into one
After setting 2g of developer on this magnet roll, place the magnet at a distance of 0cm1l.
The dust meter reads the toner particles generated when rotating at 0 rpm as dust, and calculates the number of counts per minute c.
Display in ps.

If the amount of scattering obtained here is 300 cpm or less, ○, 50
A three-level evaluation was performed, with Δ being 0 cpm or less and × being more than 500 cpm. A value of 6977 or higher is practically usable, but a value of ◯ is desirable.

Furthermore, the developer obtained here is placed in an EP-8600 developing device (a device in which a photoconductor manufactured by Minolta Camera Co., Ltd. has been modified so that it can use a chargeable toner instead of a laminated organic photoconductor).
No development was performed, and only the developing device was allowed to idle for 10 hours, and the amount of charge was measured after 1, 5, and 10 hours, and the cohesiveness of the developer was evaluated.

Table 2 shows the measurement results of the amount of charge and the amount of scattering.

Evaluation of developer cohesiveness> Take 30 g of developer, place it on a mesh with an opening of 106 μm, and sieve it for 1 minute with a vibrating sieve.
Evaluation was carried out by measuring the amount of residual developer.

Residual amount 0-1wt% ○ (Good) 1-5wt% △ (acceptable) 5～ wt% × (not allowed) The evaluation was conducted in three stages.

When aggregates occur within the developing device, the image quality deteriorates, and if the problem becomes worse, problems occur in driving the developing device itself.

The results are shown in Table 2.

Evaluation of heat resistance: Put the toner in a glass bottle and put it in a hot air dryer at 50℃7.
After storage for 2 hours, the degree of aggregation was visually judged and ranked as follows. The results are shown in Table 2.

○: No aggregates observed. Good: Some aggregates are observed, but the amount is very small or can be easily broken up with a light force. Fair: Agglomerates were observed and the aggregates were not broken up by light force. Image quality evaluation: Impossible for practical use After mixing and stirring for 10 hours, an image was produced using a developer and a standard chart from Dataquest.

At this time, the texture of the image, especially the half-density area (uncolored solid area on the chart), and back blanking were performed. A rating of 6977 or above is practically usable, but a rank of ○ is desirable.

The results are shown in Table 2.

(Hereinafter, blank space) Visually evaluate the toner fog in the loud area, and if the charge control agent is a monopolymer, the seven points used for the evaluation are the seven points of the thermoplastic resin used for the charge control agent.
In the case of a copolymer, evaluation was performed using a monomer mixture combined at a specific content, or a monomer as a main component, as a solvent.

This evaluation is styrene-acrylic resin → styrene monomer acrylic resin → main component acrylic monomer polyester resin →
This was done using ethylene glycol. Even when using other resins, it is desirable to evaluate them based on the above concept.

Charge control agent 500m5 for 100g of prescribed seven
The presence of insoluble components when dispersed, preferably 1
If an insoluble component is present when dispersed at 250 g/g, it can be used in the present invention, and the solubility was ranked as follows.

Solubility rank A charge control agent of 250 mA is poorly soluble in 100g of NATSUMA: A charge control agent of 500++ IgB is poorly soluble in 100g of NATSUMA: More than TE500IIIgc is soluble in 100g of NATSUMA: Table 3 shows the evaluation results of the solubility rank of the charge control agent used in each example.

(Hereinafter referred to as margins) Effects of the Invention The toner of the present invention has excellent charge build-up and stability, and even when subjected to high-speed development, has excellent charge stability and aggregation resistance under strong stirring.

The toner of the present invention is particularly effective as a positively charged toner,
Clear color images without color turbidity can be formed.

Claims (1)

[Claims] 1. At least a colorant, a thermoplastic resin, and the following general formula [
A toner for developing electrostatic images characterized by comprising a charge control agent selected from the group consisting of [I] to [VI] and non-magnetic inorganic fine particles; General formula [I]; ▲ Numerical formulas, chemical formulas, tables, etc. ▼[I] [In the formula, R_1, R_2 and R_3 represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and may be the same or different; M is Zn, F
represents a metal such as e, Co, Ni, Cu or Hg; X represents a halogen atom or a monovalent ionic residue; n_1 represents 2
, 4, and 6, and if M is Fe or Ni, it is 2.
or 4, if M is Cu or Co, 2, 4 or 6, M
is 2 for Zn and Hg. ]; General formula [II]; ▲Mathematical formula, chemical formula, table, etc. are available▼[II] [In the formula, R_4, R_5 and R_6 represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. , may be the same or different: M is Zn, F
Represents e, Co, Ni, Cu, Cr or Hg. ] Imidazole metal compound represented by general formula [III]; ▲Mathematical formula, chemical formula, table, etc.▼[III] [In the formula, R_7 is an alkyl group having a carbon number of C_8 to C_3_0, R_8 and R_9 are hydrogen atoms , represents a lower alkyl group, an aralkyl group or an aryl group, and each may be the same or different. ] Imidazole derivative represented by general formula [IV]; ▲ Numerical formula, chemical formula, table, etc. ▼ [IV] [In the formula, R_1_0 and R_1_1 represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and are may be different. ] Imidazole derivative represented by General formula [V]; ▲ Numerical formula, chemical formula, table, etc. ▼ [V] [In the formula, R_1_2, R_1_3 and R_1_4 represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, Each may be the same or different;
n_2 represents an integer of 1 or more. ] Imidazole derivative general formula [VI]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼[VI] They each represent a good aryl group and may be the same or different. ;R_1_7 represents an alkyl group, an aralkyl group, or an aryl group, and each group may have a substituent].